Method for producing a multicomponent system which can be thermally hardened and hardened by actinic radiation and the use thereof

ABSTRACT

A process for preparing a multicomponent system curable thermally and with actinic radiation (dual cure), where
     (A) at least one component comprising at least one constituent (A1) containing per molecule at least two isocyanate-reactive functional groups, and   (B) one component containing one polyisocyanate (B1), are mixed with one another, which comprises mixing component (A) and/or component (B), shortly before their mixing, with one further liquid component (C) comprising   (C1) one constituent which is curable with actinic radiation and contains per molecule at least two functional groups which contain bond which can be activated with actinic radiation, and/or   (C2) one constituent which is curable thermally and with actinic radiation and contains per molecule at least one functional group which contains at least one bond which can be activated with actinic radiation, and containing per molecule at least one isocyanate-reactive functional group or containing at least one isocyanate group, and subsequently mixing and homogenizing components (A/C) and (B), (A) and (B/C) or (A/C) and (B/C).

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a National Phase Application of Patent ApplicationPCT/EP01/11314 filed on 1 Oct. 2001, which claims priority to DE 100 48849.8, filed on 2 Oct. 2000.

The present invention relates to a novel process for producing amulticomponent system curable thermally and with actinic radiation. Thepresent invention additionally relates to a novel multicomponent systemcurable thermally and with actinic radiation. Furthermore, the presentinvention relates to the use of the novel multicomponent system and/orof the multicomponent system produced in accordance with the novelprocess as a coating material, adhesive or sealing compound. The presentinvention further relates to the use of the coating materials forautomotive OEM finishing, automotive refinishing, the coating offurniture, doors, windows or constructions in the interior and exteriorsector, and also for industrial coating, including coil coating,container coating and the coating or impregnation of electricalcomponents.

Here and below, actinic radiation is electromagnetic radiation such asnear infrared (NIR), visible light, UV radiation or x-rays, especiallyUV radiation, or corpuscular radiation such as electron beams.

Among those in the art, curing with heat and actinic radiation is alsoreferred to for short as dual cure.

A dual-cure multicomponent system is known, for example, from EuropeanPatent Application EP 0 928 800 A1. It comprises a urethane(meth)acrylate containing free isocyanate groups and (meth)acryloylgroups, a photoinitiator and an isocyanate-reactive compound, especiallya polyol or polyamine. Although this dual-cure coating material offersthe possibility of varying the profiles of properties of coatingmaterial and coating and of tailoring them to different end uses, itsflash-off time is still too long and its initial hardness in the shadowzones of three-dimensional substrates of complex shape, which are notreached by the actinic radiation without the use of relatively complexapparatus, is too low.

Moreover, dual-cure multicomponent systems of this kind, alongside manyother, non-polyisocyanate-based dual-cure multi- and mono-componentsystems are known from German Patent Application DE 198 18 735 A1. Theadvantages set out in the patent application, however, which arepurportedly possessed by all of the systems described therein, stop atgeneral indications and are not reinforced by a specific example.

The processes for preparing the known dual-cure multicomponent systemshave the disadvantage that it is necessary to lay down the compositionof the dual-cure multicomponent systems from the outset; subsequentvariations are possible only with difficulty and may lead to adeterioration in the profile of performance properties, such that thedual-cure multicomponent systems in question are no longer suitable fora demanding utility such as automotive refinish.

Overall, the known processes are wanting in terms of the necessarybreadth of variation, and flexibility. In the context of automotiverefinish, for example, the thermally curable multicomponent clearcoatmaterials already present in a workshop have not to date been able to beformulated as dual-cure multicomponent clearcoat materials by addingcomponents curable with actinic radiation when a sudden need arises.

It is an object of the present invention to find a new process forpreparing dual-cure multicomponent systems which makes it possible,starting from conventional multicomponent systems known per se, in asimple manner to prepare dual-cure multicomponent systems of any of avery wide variety of compositions and with any of a very wide variety ofamounts of bonds which can be activated with actinic radiation.Furthermore, the dual-cure multicomponent systems prepared by thisprocedure should have a profile of performance properties which is atleast comparable with if not indeed exceeding that of dual-curemulticomponent systems prepared in a customary and known manner. Inparticular, the coatings produced therewith should have a high initialhardness, even in the problematic shadow zones of three-dimensionalsubstrates of complex shape.

A further object of the present invention is to find a new dual-curemulticomponent system which does not now have the disadvantages of theprior art but which instead has a short flash-off time. Furthermore, thecoatings produced therewith should have a high initial hardness, even inthe problematic shadow zones of three-dimensional substrates of complexshape.

A further intention is that the new dual-cure multicomponent systemand/or the dual-cure multicomponent system prepared by the new processshould be suitable both as a coating material and also as an adhesiveand sealing compound.

Moreover, the coating material which is new or prepared by the newprocess should be outstandingly suitable for automotive OEM finishing,automotive refinishing, the coating of furniture, doors, windows orconstructions in the interior and exterior sector, and also forindustrial coating, including coil coating, container coating and thecoating or impregnation of electrical components.

The coatings, adhesive films and seals produced from the dual-curemulticomponent system prepared by the new process and/or from the newdual-cure multicomponent system should have a high scratch resistance,very good chemical, gasoline, solvent and etch resistance and alsoweathering stability, and should not exhibit any cracks.

The adhesive films and seals should exhibit long-term bond strength and,respectively, a long-term sealing capacity even under extreme and/orrapidly changing climatic conditions.

The coatings should further be outstandingly suitable as clearcoats aspart of multicoat color and/or effect coating systems. The newclearcoats should have a high initial hardness, even in the problematicshadow zones of three-dimensional substrates of complex shape.

Accordingly, we have found the novel process for preparing amulticomponent system curable thermally and with actinic radiation (dualcure), where

-   (A) at least one component comprising at least one constituent    containing per molecule on average at least two isocyanate-reactive    functional groups, and-   (B) at least one component comprising at least one polyisocyanate,    are mixed with one another, characterized in that component (A)    and/or component (B) is or are mixed, shortly before their mixing,    with at least one further liquid component (C) comprising-   (C1) at least one constituent which is curable with actinic    radiation and contains per molecule on average at least two    functional groups which contain at least one bond which can be    activated with actinic radiation, and/or-   (C2) at least one constituent which is curable thermally and with    actinic radiation and contains on average per molecule at least one    functional group which contains at least one bond which can be    activated with actinic radiation, and containing on average per    molecule at least one isocyanate-reactive functional group or    containing on average at least one isocyanate group,    and subsequently components (A/C) and (B), (A) and (B/C) or (A/C)    and (B/C) are mixed and homogenized.

In the text below, the novel process for preparing a multicomponentsystem curable thermally and with actinic radiation (dual cure) isreferred to as the “process of the invention”.

We have also found the novel multicomponent system curable thermally andwith actinic radiation (dual cure) comprising

-   (A) at least one component comprising at least one thermally curable    constituent (A1) containing per molecule on average at least two    isocyanate-reactive functional groups,-   (B) at least one component comprising a polyisocyanate (B1), and-   (C) at least one reactive diluent which is curable with actinic    radiation and contains per molecule at least 5 bonds which can be    activated with actinic radiation, the reactive diluent (C) not being    introduced by way of a thixotropic agent.

In the text below; the novel multicomponent system curable thermally andwith actinic radiation (dual cure) is referred to as the “multicomponentsystem of the invention”.

The component (A) suitable for the process of the invention and,respectively, for the multicomponent system of the invention comprisesat least one constituent (A1) containing per molecule on average atleast two, in particular at least three, isocyanate-reactive functionalgroups.

Examples of suitable isocyanate-reactive functional groups are thiol,primary or secondary amino, imino or hydroxyl groups, especiallyhydroxyl groups.

The constituent (A1) may be of low molecular mass, oligomeric orpolymeric. Preferably it is oligomeric or polymeric.

The basic structures of the low molecular mass constituents (A1) are notcritical but instead may derive from any of a very wide variety oforganic compound classes. Examples of suitable classes of compound arealkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl,cycloalkylaryl, arylalkyl and/or arylcycloalkyl compounds with orwithout heteroatoms such as oxygen, nitrogen, sulfur, silicon orphosphorus and optionally carrying further substituents which, however,must not react during the preparation of the constituents, their storageand/or their use with the bonds which can be activated with actinicradiation.

The basic structures of the oligomeric or polymeric constituents (A1)are likewise not critical and may derive from any of a wide variety ofoligomer and polymer classes. Examples of suitable oligomer and polymerclasses are random, alternating and/or block, linear and/or branchedand/or comb addition (co)polymers of ethylenically unsaturated monomers,or polyaddition resins and/or polycondensation resins. Regarding theseterms, reference is made for further details to Römpp Lexikon Lacke undDruckfarben, Georg Thieme Verlag, Stuttgart, N.Y., 1998, page 457,“Polyaddition” and “Polyaddition resins (polyadducts)”, and also pages463 and 464, “Polycondensates”, “Polycondensation” and “Polycondensationresins”. As regards any substituents which may be present, the remarksmade above apply accordingly.

Examples of highly suitable addition (co)polymers (A1) arepoly(meth)acrylates and partially hydrolyzed polyvinyl esters.

Examples of highly suitable polyaddition resins and/or polycondensationresins (A1) are polyesters, alkyds, polyurethanes, polylactones,polycarbonates, polyethers, epoxy resin-amine adducts, polyureas,polyamides or polyimides.

In accordance with the invention, the (meth)acrylate copolymers,especially those containing hydroxyl groups, have particular advantagesand in accordance with the invention are used with particular preferenceas constituents (A1).

The (meth)acrylate copolymers (A1) are polymers which are known per se.Their preparation has no special features as to method but instead takesplace with the aid of the methods, customary and known in the plasticsfield, of continuous or batchwise free-radically initiatedcopolymerization in bulk, solution, emulsion, miniemulsion ormicroemulsion under atmospheric pressure or superatmospheric pressure instirred vessels, autoclaves, tube reactors, loop reactors or Taylorreactors at temperatures from 50 to 200° C.

Examples of suitable (meth)acrylate copolymers (A1) and copolymerizationmethods are described in patent applications DE 197 09 465 A1, DE 197 09476 A1, DE 28 48 906 A1, DE 195 24 182 A1, DE 198 28 742 A1, DE 196 28143 A1, DE 196 28 142 A1, EP 0 554 783 A1, WO 95/27742, WO 82/02387 andWO 98/02466.

Their hydroxyl number is preferably 70-200, more preferably 80-170 andespecially 90 or 150 mg KOH/g.

In component (A), the constituents (A1) are present in widely varyingamounts. Preferably, the component comprises the constituents (A1) in anamount of from 40 to 95, more preferably from 45 to 95 and in particularfrom 40 to 90% by weight, based in each case on component (A).

Furthermore, component (A) of the multicomponent system may furthercomprise customary and known additives in effective amounts. Theessential factor is that the additives do not inhibit or prevententirely the dual-cure crosslinking reactions.

Examples of suitable additives are nanoparticles, reactive diluentscurable thermally low-boiling organic solvents and high-boiling organicsolvents (“long solvents”), water, UV absorbers, light stabilizers,free-radical scavengers, thermally labile free-radical initiators,photoinitiators and photo-coinitiators, crosslinking agents as used inone-component systems, thermal crosslinking catalysts, devolatilizers,slip additives, polymerization inhibitors, defoamers, emulsifiers,wetting agents, dispersants, adhesion promoters, leveling agents,film-forming auxiliaries, sag control agents (SCAs), rheology controladditives (thickeners), flame retardants, siccatives, dryers,antiskinning agents, corrosion inhibitors, waxes, flatting agents,precursors of organically modified ceramic materials, or additionalbinders.

Examples of suitable thermally curable reactive diluents arepositionally isomeric diethyloctanediols or hydroxyl-containinghyperbranched compounds or dendrimers, as described for example inGerman Patent Applications DE 198 05 421 A1, DE 198 09 643 A1, and DE198 40 405 A1.

Examples of suitable low-boiling organic solvents and high-boilingorganic solvents (“long solvents”) are ketones such as methyl ethylketone, methyl isoamyl ketone or methyl isobutyl ketone, esters such asethyl acetate, butyl acetate, ethyl ethoxypropionate, methoxypropylacetate or butyl glycol acetate, ethers such as dibutyl ether orethylene glycol, diethylene glycol, propylene glycol, dipropyleneglycol, butylene glycol or dibutylene glycol dimethyl, diethyl ordibutyl ether, N-methylpyrrolidone or xylenes or mixtures of aromaticand/or aliphatic hydrocarbons such as Solventnaphtha®, mineral spirit135/180, dipentenes or Solvesso®.

Examples of suitable thermally labile free-radical initiators areorganic peroxides, organic azo compounds or C-C-cleaving initiators suchas dialkyl peroxides, peroxocarboxylic acids, peroxodicarbonates, orperoxide esters, hydroperoxides, ketone peroxides, azo dinitriles orbenzpinacol silyl ethers.

Examples of suitable crosslinking catalysts are dibutyltin dilaurate,dibutyltin dioleate, lithium decanoate, zinc octoate or bismuth saltssuch as bismuth lactate or bismuth dimethylolpropionate.

Examples of suitable photoinitiators and coinitiators are described inRömpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart,1998, pages 444 to 446.

Examples of suitable additional crosslinking agents as used inone-component systems are amino resins, as described for example inRömpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, 1998, page 29,“Amino resins”, in the text book “Lackadditive” [Additives for Coatings]by Johan Bieleman, Wiley-VCH, Weinheim, N.Y., 1998, pages 242 ff., inthe book “Paints, coatings and solvents”, second, completely revisededition, D. Stoye and W. Freitag (eds.), Wiley-VCH, Weinheim, N.Y.,1998, pages 80 ff., in patents U.S. Pat. No. 4,710,542 A1 and EP-B-0 245700 A1, and in the article by B. Singh and coworkers,“Carbamylmethylated Melamines, Novel Crosslinkers for the CoatingsIndustry” in Advanced Organic Coatings Science and Technology Series,1991, Volume 13, pages 193 to 207; carboxyl-containing compounds orresins, as described for example in patent DE 196 52 813 A1; resins orcompounds containing epoxide groups, as described for example in patentsEP 0 299 420 A1, DE 22 14 650 B1, DE 27 49 576 B1, U.S. Pat. No.4,091,048 A and U.S. Pat. No. 3,781,379 A; blocked polyisocyanates, asdescribed for example in patents U.S. Pat. No. 4,444,954 A, DE 196 17086 A1, DE 196 31 269 A1, EP 0 004 571 A1 and EP 0 582 051 A1; and/ortris(alkoxycarbonylamino)triazines as described in patents U.S. Pat. No.4,939,213 A, U.S. Pat. No. 5,084,541 A, U.S. Pat. No. 5,288,865 A and EP0 604 922 A1.

Examples of suitable devolatilizers are diazadicycloundecane andbenzoin.

Examples of suitable emulsifiers are nonionic emulsifiers, such asalkoxylated alkanols, polyols, phenols and alkylphenols, or anionicemulsifiers such as alkali metal salts or ammonium salts ofalkanecarboxylic acids, alkanesulfonic acids, and sulfo acids ofalkoxylated alkanols, polyols, phenols and alkylphenols.

Examples of suitable wetting agents are siloxanes, fluorine compounds,carboxylic monoesters, phosphoric esters, polyacrylic acids and theircopolymers, or polyurethanes.

An example of a suitable adhesion promoter is tricyclodecanedimethanol.

Examples of suitable film-forming auxiliaries are cellulose derivativessuch as cellulose acetobutyrate (CAB).

Examples of suitable transparent fillers are those based on silicondioxide, aluminum oxide or zirconium oxide; for further details,reference is made to Römpp Lexikon Lacke und Druckfarben, Georg ThiemeVerlag, Stuttgart, 1998, pages 250 to 252.

Examples of suitable sag control agents are ureas, modified ureas and/orsilicas, as described for example in the literature references EP 0 192304 A1, DE 23 59 923 A1, DE 18 05 693 A1, WO 94/22968, DE 27 51 761 C1,WO 97/12945 or “farbe+lack”, November 1992, pages 829 ff.

Examples of suitable rheology control additives are those known frompatents WO 94/22968, EP 0 276 501 A1, EP 0 249 201 A1 and WO 97/12945;crosslinked polymeric microparticles, as disclosed for example in EP 0008 127 A1; inorganic phyllosilicates such as aluminum-magnesiumsilicates, sodium-magnesium and sodium-magnesium-fluorine-lithiumphyllosilicates of the montmorillonite type; silicas such as Aerosils;or synthetic polymers containing ionic and/or associative groups such aspolyvinyl alcohol, poly(meth)acrylamide, poly(meth)acrylic acid,poly-vinylpyrrolidone, styrene-maleic anhydride copolymers orethylene-maleic anhydride copolymers and their derivatives orhydrophobically modified ethoxylated urethanes or polyacrylates.

An example of a suitable flatting agent is magnesium stearate.

Examples of suitable precursors of organically modified ceramicmaterials are hydrolyzable organometallic compounds, especially ofsilicon and aluminum.

Further examples of the above-listed additives and also examples ofsuitable UV absorbers, free-radical scavengers, leveling agents, flameretardants, siccatives, dryers, antiskinning agents, corrosioninhibitors and waxes (B) are described in detail in the textbook“Lackadditive” by Johan Bieleman, Wiley-VCH, Weinheim, N.Y., 1998.

The preparation of component (A) for use in accordance with theinvention has no special features but instead takes place in a customaryand known manner by mixing of the above-described constituents inappropriate mixing equipment such as stirred vessels, dissolvers,stirred mills or extruders.

Component (B) of the multicomponent system of the invention comprises atleast one polyisocyanate (B1).

The polyisocyanates (B1) contain on average per molecule at least 2.0,preferably more than 2.0, and in particular more than 3.0 isocyanategroups. Basically, there is no upper limit on the number of isocyanategroups; in accordance with the invention, however, it is of advantage ifthe number does not exceed 15, preferably 12, with particular preference10, with very particular preference 8.0, and in particular 6.0.

Examples of suitable polyisocyanates (B1) are isocyanato-containingpolyurethane prepolymers which may be prepared by reacting polyols withan excess of diisocyanates and are preferably of low viscosity.

Examples of suitable diisocyanates are isophorone diisocyanate (i.e.,5-isocyanato-1-isocyanatomethyl-1,3,3-trimethylcyclohexane),5-isocyanato-1-(2-isocyanatoeth-1-yl)-1,3,3-trimethylcyclohexane,5-isocyanato-1-(3-isocyanatoprop-1-yl)-1,3,3-trimethylcyclohexane,5-isocyanato-(4-isocyanatobut-1-yl)-1,3,3-trimethylcyclohexane,1-isocyanato-2-(3-isocyanatoprop-1-yl)-cyclohexane,1-isocyanato-2-(3-isocyanatoeth-1-yl)cyclohexane,1-isocyanato-2-(4-isocyanatobut-1-yl)-cyclohexane,1,2-diisocyanatocyclobutane, 1,3-diisocyanatocyclobutane,1,2-diisocyanatocyclopentane, 1,3-diisocyanatocyclopentane,1,2-diisocyanatocyclohexane, 1,3-diisocyanatocyclohexane,1,4-diisocyanatocyclohexane, dicyclohexylmethane 2,4′-diisocyanate,trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylenediisocyanate, hexamethylene diisocyanate (HDI), ethylethylenediisocyanate, trimethylhexane diisocyanate, heptamethylene diisocyanateor diisocyanates derived from dimeric fatty acids, as sold under thecommercial designation DDI 1410 by the company Henkel and described inpatents WO 97/49745 and WO 97/49747, especially2-heptyl-3,4-bis(9-isocyanatononyl)-1-pentylcyclohexane, or 1,2-, 1,4-or 1,3-bis(isocyanatomethyl)cyclohexane, 1,2-, 1,4- or1,3-bis(2-isocyanatoeth-1-yl)cyclohexane,1,3-bis(3-isocyanatopropy-1-yl)cyclohexane, 1,2-, 1,4- or1,3-bis(4-isocyanatobut-1-yl)cyclohexane or liquidbis(4-isocyanatocyclohexyl)methane with a trans/trans content of up to30% by weight, preferably 25% by weight and in particular 20% by weight,as described in patent applications DE 44 14 032 A1, GB 1220717 A1, DE16 18 795 A1 and DE 17 93 785 A1, preferably isophorone diisocyanate,5-isocyanato-1-(2-isocyanatoeth-1-yl)-1,3,3-trimethylcyclohexane,5-isocyanato-1-(3-isocyanatoprop-1-yl)-1,3,3-trimethylcyclohexane,5-isocyanato-(4-isocyanatobut-1-yl)-1,3,3-trimethylcyclohexane,1-isocyanato-2-(3-isocyanatoprop-1-yl)cyclohexane,1-isocyanato-2-(3-isocyanatoeth-1-yl)cyclohexane,1-isocyanato-2-(4-isocyanatobut-1-yl)cyclohexane or HDI, especially HDI.

It is also possible to use polyisocyanates (B1) containing isocyanurate,biuret, allophanate, iminooxadiazinedione, urethane, urea, carbodiimideand/or uretdione groups, which are prepared in a customary and knownmanner from the diisocyanates described above. Examples of suitablepreparation techniques and polyisocyanates are known, for example, frompatents CA 2,163,591 A, U.S. Pat. No. 4,419,513, U.S. Pat. No. 4,454,317A, EP 0 646 608 A, U.S. Pat. No. 4,801,675 A, EP 0 183 976 A1, DE 40 15155 A1, EP 0 303 150 A1, EP 0 496 208 A1, EP 0 524 500 A1, EP 0 566 037A1, U.S. Pat. No. 5,258,482 A1, U.S. Pat. No. 5,290,902 A1, EP 0 649 806A1, DE 42 29 183 A1 and EP 0 531 820 A1.

The amount of the polyisocyanates (B1) in component (B) may vary widely.Primarily it is guided by the viscosity necessary for mixing with theother components. Preferably, the amount is from 20 to 80, morepreferably from 30 to 70, and in particular from 35 to 65% by weight,based on component (B). Component (B) preferably further comprises atleast one of the above-described organic solvents.

In accordance with the invention, component (A) and/or component (B) aremixed shortly prior to their mixing, before application, with at leastone further liquid component (C).

Component (C) comprises at least one constituent (C1) which is curablewith actinic radiation and contains on average per molecule at least twofunctional groups having at least one bond which can be activated withactinic radiation.

Examples of suitable bonds which can be activated with actinic radiationare carbon-hydrogen single bonds or carbon-carbon, carbon-oxygen,carbon-nitrogen, carbon-phosphorus or carbon-silicon single bonds ordouble bonds. Of these, the double bonds, especially the carbon-carbondouble bonds (“double bonds”), are employed with preference.

Very suitable double bonds are present, for example, in (meth)acrylate,ethacrylate, crotonate, cinnamate, vinyl ether, vinyl ester,ethenylarylene, dicyclopentadienyl, norbornenyl, isoprenyl, isoprenyl,isopropenyl, allyl or butenyl groups; ethenylarylene ether,dicyclopentadienyl ether, norbornenyl ether, isoprenyl ether,isopropenyl ether, allyl ether or butenyl ether groups; orethenylarylene ester, dicyclopentadienyl ester, norbornenyl ester,isoprenyl ester, isopropenyl ester, allyl ester or butenyl ester groups.Of these, (meth)acrylate groups, especially acrylate groups, are ofparticular advantage and are therefore used with very particularpreference in accordance with the invention.

The constituent (C1) may be of low molecular mass, oligomeric orpolymeric. Preferably it is of low molecular mass.

The basic structures of the oligo- or polymeric constituents (C1) arenot critical, instead it is possible to use the basic structuresdescribed above for the constituent (A1).

Even the basic structures of the low molecular mass constituents (C1)are not critical but instead may derive from any of a wide variety oforganic compound classes. Examples of suitable classes of compounds arealkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl,cycloalkylaryl, arylalkyl and/or arylcycloalkyl compounds with orwithout heteroatoms such as oxygen, nitrogen, sulfur, silicon orphosphorus and optionally carrying further substituents which, however,must not react during the preparation of the constituents (C1), theirstorage and/or their use with the bonds which can be activated withactinic radiation.

Examples of suitable constituents (C1) are the reactive diluents curablewith actinic radiation, as described for example in Römpp Lexikon Lackeund Druckfarben, Georg Thieme Verlag, Stuttgart, N.Y., 1998, on page 491under the entry “Reactive diluents”, or in column 7, lines 1 to 26 of DE198 18 715 A1.

Particularly appropriate constituents (C1) are reactive diluents curablewith actinic radiation and having at least 5, especially 5, of theabove-described groups which can be activated with actinic radiation,especially acrylate groups. One example of such a reactive diluent (C1)is pentaerythritol pentaacrylate. These reactive diluents (C1),especially pentaerythritol pentaacrylate (C1), are not introduced by wayof thixotropic agents.

The amount of the constituent (C1) in component (C) may vary widely,preferably it is from 30 to 90%, more preferably from 40 to 80%, and inparticular from 50 to 70% by weight, based in each case on component(C). Furthermore, component (C) may further comprise at least one otherof the additives described above, provided they do not react with theconstituent (C1).

Component (C) containing the above-described constituent (C1) ispreferably mixed with component (A), subsequent to which the resultantcomponent (A/C) is mixed and homogenized with component (B) or withcomponent (B/C).

Instead of the above-described constituent (C1) or in addition to it,component (C) comprises at least one constituent (C2).

The constituent (C2) comprises on average per molecule

-   -   at least one, in particular at least two, of the above-described        functional groups which can be activated with actinic radiation,        and    -   at least one, in particular at least two, of the above-described        isocyanate-reactive functional groups, or    -   at least one, especially at least two, isocyanate groups.        Examples of suitable basic structures for the constituents (C2)        which contain at least one, in particular at least two, of the        above-described isocyanate-reactive functional groups are the        above-described low molecular mass, oligomeric and polymeric        basic structures. Of these, the polyurethanes (C2) are of        particular advantage and are therefore used with particular        preference.

The preparation of polyurethanes (C2) having terminal and/or lateraldouble bonds has no special features in terms of its method but insteadis described in detail in patent applications and patents DE 196 45 761A, WO 98/10028, EP 0 742 239 A1, EP 0 661 321 B1, EP 0 608 021 B1, EP 0447 998 B1, and EP 0 462 287 B1. Moreover, these constituents arecommercially customary products and are sold, for example, under thebrand name Rahn® 99-664 by the company Rahn.

In component (C), the amount of constituent (C2) may vary widely.Preferably, it is from 30 to 90, more preferably from 40 to 80, and inparticular from 50 to 70% by weight, based in each case on component(C). Furthermore, the component (C) in question may also comprise atleast one other of the above-described additives, provided they do notreact with the constituent (C2).

Component (C) comprising the above-described constituent (C2) is mixedwith component (A), subsequent to which the resultant component (A/C) ismixed and homogenized with component (B) or with component (B/C).

Instead of the above-described constituent (C2), component (C) maycomprise at least one constituent (C2) containing isocyanate groups.

These constituents (C2) are, as is known, obtainable by reacting theabove-described diisocyanates and polyisocyanates (B1) with compoundscontaining at least one, especially one, of the above-describedisocyanate-reactive functional groups and at least one, especially one,bond which can be activated with actinic radiation. Examples of suitablecompounds of this kind are

-   -   2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl,        3-hydroxybutyl, 4-hydroxybutyl, bis(hydroxy-methyl)cyclohexane,        neopentyl glycol, diethylene glycol, dipropylene glycol,        dibutylene glycol, or triethylene glycol acrylate, methacrylate,        ethacrylate, crotonate, cinnamate, vinyl ether, allyl ether,        dicyclopentadienyl ether, norbornenyl ether, isoprenyl ether,        isopropenyl ether or butenyl ether;    -   trimethylolpropane di-, glycerol di-, trimethylol-ethane di-,        pentaerythritol tri- or homopenta-erythritol tri-acrylate,        -methacrylate, -ethacrylate, -crotonate, -cinnamate, -vinyl        ether, -allyl ether, -dicyclopentadienyl ether, -norbornenyl        ether, -isoprenyl ether, -isopropenyl ether or -butenyl ether;        or    -   reaction products of cyclic esters, such as        epsilon-caprolactone, for example, and the above-described        hydroxyl-containing monomers; or    -   2-aminoethyl (meth)acrylate and/or 3-aminopropyl (meth)acrylate.

Viewed in terms of its method, the preparation of these constituents(C2) has no special features but instead takes place as described, forexample, in European Patent Application EP 0 928 800 A1.

The amount of this constituent (C2) in component (C) may vary widely.Preferably it is from 60 to 95, more preferably from 70 to 95, and inparticular from 75 to 85% by weight, based in each case on component(C). Furthermore, component (C) in question may also comprise at leastone of the above-described additives, provided these do not react withisocyanate groups (C2).

Component (C) containing the isocyanato-containing constituent (C2) ismixed and homogenized with component (B), subsequent to which theresultant component (B/C) is mixed and homogenized with component (A) orwith component (A/C).

Viewed in terms of its method, the mixing of components (A/C) and (B),(A) and (B/C) or (A/C) and (B/C) has no special features but instead isconducted with the aid of the customary and known, above-describedmixing apparatus and mixing processes or by means of customarytwo-component or multicomponent metering and mixing equipment. Ideally,mixing takes place by hand, where the viscosity of the componentspermits.

The volume ratio of components (A):(C) in the process of the inventionmay vary widely. If component (C) exclusively is added to component (B),this ratio may be mathematically infinite. Otherwise, the ratio (A):(C)is preferably from 2:1 to 1:2, preferably from 1.5:1 to 1:1.5, and inparticular from 1.2:1 to 1:1.2.

The volume ratio of components (B):(C) in the process of the inventionmay likewise vary very widely. If component (C) exclusively is added tocomponent (A), this ratio may be mathematically infinite. Otherwise, theratio (B):(C) is preferably from 2:1 to 1:2, preferably from 1.5:1 to1:1.5, and in particular from 1.2:1 to 1:1.2.

Furthermore, it is possible for the volume ratio of components(A):(B/C), (A/C):(B) or (A/C):(B/C) in the process of the invention tovary very widely. Preferably these ratios are from 5:1 to 1:5,preferably from 4:1 to 1:4, and in particular from 3:1 to 1:3.

The matter of which volume ratios are employed is guided primarily bythe functionality and concentration of the above-described reactiveconstituents of the components. The skilled worker will therefore easilybe able to determine the optimum volume ratio for each specific case, onthe basis of his or her knowledge in the art, possibly with theassistance of simple rangefinding tests.

It is a very particular advantage of the process of the invention thatit can be used, starting from a conventional, thermally curablemulticomponent system, to prepare dual-cure multicomponent systems in asimple manner when the need suddenly arises, these systems being of verydifferent material composition and functionality.

The dual-cure multicomponent systems prepared with the aid of theprocess of the invention, especially the multicomponent system of theinvention, comprising

-   -   at least one, especially one, component (A) comprising at least        one of the above-described constituents (A1),    -   at least one, especially one, component (B) comprising at least        one of the above-described polyisocyanates (B1), and    -   at least one, especially one, component (C) comprising at least        one of the above-described reactive diluents (C1) containing at        least 5 bonds per molecule which can be activated with actinic        radiation, the reactive diluent (C1) not being introduced by way        of a thixotropic agent,        may therefore be put to a very wide variety of end uses. They        are preferably used as coating materials, adhesives and sealing        compounds.

The coating materials, adhesives and sealing compounds are used toproduce coats, adhesive films and seals on and/or in primed and unprimedsubstrates. In particular, the coating materials are used to produceclearcoats, especially clearcoats in multicoat color and/or effectcoating systems.

In terms of method, the application of the clearcoat materials has nospecial features but instead may take place by any customary applicationmethod, such as spraying, knifecoating, brushing, flowcoating, dipping,trickling or rolling, for example. It is preferred to employ sprayapplication methods, such as compressed air spraying, airless spraying,high-speed rotation, electrostatic spray application (ESTA), alone or inconjunction with hot spray applications such as hot-air spraying, forexample.

Suitable substrates are surfaces which are not damaged by curing of thecoating materials, adhesives and/or sealing compounds present thereonusing heat and actinic radiation; examples are metals, plastics, wood,ceramic, stone, textile, fiber composites, leather, glass, glass fibers,glass wool, rockwool, mineral-bound and resin-bound building materials,such as plasterboard and cement slabs or roof tiles, and also assembliesof these materials.

Accordingly, the coating materials, adhesives and sealing compounds arealso suitable for applications outside of automotive OEM finishing andautomotive refinishing. In this context they are particularly suitablefor the coating, bonding and/or sealing of furniture, windows, doors,constructions in the interior and exterior sector, and for industrialcoating, including coil coating, container coating and the impregnationor coating of electrical components. In the context of industrialcoatings, they are suitable for coating, bonding and/or sealingvirtually all parts for private or industrial use, such as radiators,domestic appliances, small metal parts such as nuts and bolts, hub caps,wheel rims, packaging, or electrical components such as motor windingsor transformer windings.

In the case of electrically conductive substrates, it is possible to useprimers which are produced in a customary and known manner from theelectrodeposition coating materials. Both anodic and cathodicelectrodeposition coating materials are suitable for this purpose, butespecially cathodic coating materials.

The electrodeposition coat or electrodeposition coating film may beovercoated with a surfacer, which is cured either alone or together withthe electrodeposition coating film (wet-on-wet technique). Overcoatingwith a surfacer takes place in particular in the regions exposed tosevere mechanical stress, such as by stonechipping, for example.

Examples of suitable cathodic electrodeposition coating materials and,where appropriate, of wet-on-wet techniques are described in Japanesepatent application 1975-142501 (Japanese laid-open specification JP52-065534 A2, Chemical Abstracts No. 87: 137427) or in patents andpatent applications U.S. Pat. No. 4,375,498 A, U.S. Pat. No. 4,537,926A, U.S. Pat. No. 4,761,212 A, EP 0 529 335 A1, DE 41 25 459 A1, EP 0 595186 A1, EP 0 074 634 A1, EP 0 505 445 A1, DE 42 35 778 A1, EP 0 646 420A1, EP 0 639 660 A1, EP 0 817 648 A1, DE 195 12 017 C1, EP 0 192 113 A2,DE 41 26 476 A1 or WO 98/07794.

Similarly, appropriate surfacers, especially aqueous surfacers, whichare also referred to as antistonechip primers or functional coats, areknown from patents and patent applications U.S. Pat. No. 4,537,926 A, EP0 529 335 A1, EP 0 595 186 A1, EP 0 639 660 A1, DE 44 38 504 A1, DE 4337 961 A1, WO 89/10387, U.S. Pat. No. 4,450,200 A, U.S. Pat. No.4,614,683 A or WO 490/26827.

It is also possible to coat, bond or seal primed or unprimed plasticsparts made, for example, from ABS, AMMA, ASA, CA, CAB, EP, UF, CF, MF,MPF, PF, PAN, PA, PE, HDPE, LDPE, LLDPE, UHMWPE, PC, PC/PBT, PC/PA, PET,PMMA, PP, PS, SB, PUR, PVC, RF, SAN, PBT, PPE, POM, PUR-RIM, SMC, BMC,PP-EPDM and UP (abbreviated codes in accordance with DIN 7728T1).Unfunctionalized and/or nonpolar substrate surfaces may be subjectedprior to coating in a known manner to a pretreatment, such as by plasmaor by flaming, or may be provided with a primer.

To produce the clearcoats, the clearcoat materials are applied to thesubstrates described above, after which the resulting clearcoat filmsare cured.

To produce the adhesive films and seals, the adhesives and sealingcompounds are applied on and/or in the above-described substrates. Inthe case of the bonding of substrates, the surfaces of two or moresubstrates that are to be bonded are preferably coated with the adhesiveof the invention, after which the surfaces in question are brought intocontact, under pressure if appropriate, and the resultant adhesive filmsare cured.

As is known, the production of a multicoat color and/or effect coatingsystem on a primed or unprimed substrate takes place by

-   (1) applying a basecoat material to the substrate,-   (2) drying and/or partly or fully curing the basecoat film,-   (3) applying a clearcoat material to the dried and/or partly cured    basecoat film or to the cured basecoat, and-   (4) conjointly curing the clearcoat film with the basecoat film, or    separately curing the clearcoat film.

Examples of suitable basecoat materials are known from patentapplications EP 0 089 497 A1, EP 0 256 540 A1, EP 0 260 447 A1, EP 0 297576 A1, WO 96/12747, EP 0 523 610 A1, EP 0 228 003 A1, EP 0 397 806 A1,EP 0 574 417 A1, EP 0 531 510 A1, EP 0 581 211 A1, EP 0 708 788 A1, EP 0593 454 A1, DE-A-43 28 092 A1, EP 0 299 148 A1, EP 0 394 737 A1, EP 0590 484 A1, EP 0 234 362 A1, EP 0 234 361 A1, EP 0 543 817 A1, WO95/14721, EP 0 521 928 A1, EP 0 522 420 A1, EP 0 522 419 A1, EP 0 649865 A1, EP 0 536 712 A1, EP 0 596 460 A1, EP 0 596 461 A1, EP 0 584 818A1, EP 0 669 356 A1, EP 0 634 431 A1, EP 0 678 536 A1, EP 0 354 261 A1,EP 0 424 705 A1, WO 97/49745, WO 97/49747, EP 0 401 565 A1, and EP 0 817684, column 5, lines 31 to 45.

In general, the surfacer film, topcoat film, basecoat film and clearcoatfilm are applied in a wet film thickness such that curing thereofresults in coats having the film thicknesses advantageous and necessaryfor their functions. In the case of the surfacer film this filmthickness is from 10 to 150, preferably from 15 to 120, with particularpreference from 20 to 100, and in particular from 25 to 90 μm, in thecase of the topcoat the film thickness is from 5 to 90, preferably from10 to 80, with particular preference from 15 to 60, and in particularfrom 20 to 50 μm, in the basecoat case it is 5 to 50, preferably 6 to40, especially preferably 7 to 30 and in particular 8 to 25 μm, and inthe case of the clearcoats it is from 10 to 100, preferably from 15 to90, with particular preference from 20 to 80, and in particular from 25to 70 μm.

The complete curing takes place after a certain flash-off time. This isused, for example, for leveling and for the degassing of the appliedfilms or for the evaporation of volatile constituents such as solventsor water. The flash-off time may be assisted and/or shortened by the useof elevated temperatures up to 40° C. and/or by blowing on the films,provided this does not entail any damage or alteration to the appliedfilms, such as premature complete crosslinking, for example. Theclearcoats of the invention have an advantageously short flash-off time,in this case, of <10, especially <6 minutes. This produces a shorteningin the process times overall.

The curing takes place with actinic radiation, especially with UVradiation, and/or electron beams. If desired, it may be supplemented byor carried out with actinic radiation from other radiation sources. Inthe case of electron beams, it is preferred to operate under an inertgas atmosphere. This may be ensured, for example, by supplying carbondioxide and/or nitrogen directly to the surface of the applied films.

In the case of curing with UV radiation as well it is possible tooperate under inert gas in order to prevent the formation of ozone.

Curing with actinic radiation is carried out using the customary andknown radiation sources and optical auxiliary measures. Examples ofsuitable radiation sources are high or low pressure mercury vapor lamps,with or without lead doping in order to open up a radiation window of upto 405 nm, or electron beam sources. Their arrangement is known inprinciple and may be adapted to the circumstances of the workpiece andthe process parameters. In the case of workpieces of complex shape suchas automobile bodies, the regions not accessible by direct radiation(shadow regions) such as cavities, folds and other structural undercutsmay be cured using point, small-area or all-round sources, inconjunction with an automatic movement device for the irradiation ofcavities or edges.

The equipment and conditions for these curing methods are described, forexample, in R. Holmes, U.V. and E.B. Curing Formulations for PrintingInks, Coatings and Paints, SITA Technology, Academic Press, London,United Kingdom 1984.

The cure may be effected in stages, i.e., by multiple exposure to lightor actinic radiation. This can also be done alternatingly, i.e., bycuring in alternation with UV radiation and electron beams.

Thermal curing as well has no special features in terms of method butinstead takes place in accordance with the customary and known methodssuch as heating in a forced air oven or irradiation with IR lamps. Asfor curing with actinic radiation, thermal curing may also take place instages. Thermal curing is preferably effected at room temperature orabove room temperature, preferably at temperatures >40° C.,preferably >50° C., for a period of from one minute to several days.

Thermal curing and curing with actinic radiation may be usedsimultaneously or in alternation. Where the two curing methods are usedin alternation, it is possible, for example, to commence with thermalcuring and end with actinic radiation curing. In other cases, it mayprove advantageous to commence and to end with actinic radiation curing.The skilled worker is able to determine the curing method which is mostadvantageous for the particular case in hand, on the basis of hisgeneral knowledge of the art with the assistance, if appropriate, ofsimple preliminary tests.

The coating materials, adhesives and sealing compounds prepared by meansof the process of the invention, and also the coating materials,adhesives and sealing compounds of the invention based on themulticomponent system of the invention, have a high solids content atlow viscosity and a long stand time.

The flash-off time of the dual-cure multicomponent systems, especiallyof the clearcoat material, before curing is very short, so that theprocess times overall are reduced.

The coats, adhesive films and seals produced using the dual-curemulticomponent systems, especially the clearcoats, have a high initialhardness even in the shadow regions of the substrates.

The resulting coatings, especially the clearcoats and the multicoatcolor and/or effect coating systems comprising them, are of highhardness, flexibility and chemical resistance, possess outstandingleveling, no runs, very good intercoat adhesion, an outstanding overallappearance, very good weathering stability, very high scratch resistanceand abrasion resistance, and also very good polishability.

The adhesive films are of high and long-term bond strength even underextreme and/or very sharply and rapidly changing climatic conditions.

The seals provide long-term and complete sealing against chemicallyaggressive substances.

Accordingly, the primed and unprimed substrates coated with at least oneof the coats, bonded with at least one of the adhesive films, and/orsealed with at least one of the seals possess, in addition to theadvantages set out above, a particularly long service life as well,which make them particularly valuable from an economic standpoint.

EXAMPLES Preparation Example 1

The Preparation of a Thermally Curable Methacrylate Copolymer

A steel reactor equipped with stirrer, reflux condenser and two feedvessels was charged with 185.6 parts by weight of ethyl epoxypropionateand this initial charge was heated with stirring to 160° C.Subsequently, a monomer mixture of 114.1 parts by weight of styrene,136.9 parts by weight of methyl methacrylate, 79.3 parts by weight ofbutyl methacrylate, 109 parts by weight of n-butyl acrylate and 164.1parts by weight of hydroxyethyl methacrylate was metered in at a uniformrate over the course of four hours. Beginning at the same time and inparallel with this monomer mixture, an initiator mixture of 35.8 partsby weight of ethyl ethoxypropionate and 36.2 parts by weight ofdi-tert-butyl peroxide was metered in at a uniform rate. After one hour,initiation was repeated at 110° C. with an initiator mixture of 5.7parts by weight of butyl acetate and 0.5 parts by weight of tert-butylperoxyethylhexanoate. Subsequently, the resultant reaction mixture washeld at 110° C. for one hour. Thereafter, at 80° C., the solution wasadjusted to a solids content of 65% by weight using butyl acetate. Theresultant solution had a viscosity of 15 dPas. The hydroxyl number ofthe methacrylate copolymer was 120 mg KOH/g.

Examples 1 to 4

The Preparation of Clearcoat Materials by the Process of the Inventionand their Use to Produce Multicoat Color and Effect Coating Systems

The clearcoat materials 1 to 4 of examples 1 to 4 were prepared bymixing the components stated in table 1.

For this purpose, in the case of example 1, components (A), (B) and(C/C1) were mixed with one another in a volume ratio of 2:1:2, component(C/C1) being mixed prior to the addition of (B) with component (A).

In the case of example 2, components (A), (B) and (C/C2) were mixed withone another in a volume ratio of 1:1:1, component (C/C2) being mixedprior to the addition of (B) with component (A).

In the case of example 3, components (A), (B) and (C/C2) were mixed withone another in a volume ratio of 4:1:1, component (C/C2) being mixedprior to the addition of (A) with component (B).

In the case of example 4, components (A), (B) and (C/C2 withoutisocyanate groups) and (C/C2 with isocyanate groups) were mixed with oneanother in a volume ratio of 2:2:1:1, component (C/C2 without isocyanategroups) having been mixed with component (A) and the component (C/C2with isocyanate groups) with component (B), after which the resultingcomponents (A/C) and (B/C) were mixed with one another and homogenized.

Subsequently, the clearcoat materials 1 to 4 of examples 1 to 4 werediluted with 10%, based on the clearcoat materials, of a diluent(solvent mixture of xylene, solvent naphtha, mineral spirit 135/180,methoxypropyl acetate, butyl acetate, butyl glycol acetate, ethylethoxypropionate and dipentenes).

TABLE 1 The material composition of components (A), (B) and (C) of theclearcoat materials 1 to 4 Clearcoat - example: Constituent 1 2 3 4Component (A): Methacrylate copolymer of 86 86 86 86 preparation example1 Butyl acetate 4.5 4.5 4.5 4.5 Ethyl ethoxypropionate 4 4 4 4 Methylisoamyl ketone 2 2 2 2 Byk ® 325^(a)) 0.3 0.3 0.3 0.3 Byk ® 358^(a))0.71 0.7 0.7 0.7 Dibutyltin dilaurate (10% in 0.5 0.5 0.5 0.5 butylacetate) Tinuvin ® 292^(b)) 1 1 1 1 Tinuvin ® 400^(b)) 1 1 1 1 Component(B): Desmodur ® N3600^(c)) 56 56 56 56 Methoxypropyl acetate 22 22 22 22Ethyl ethoxypropionate 22 22 22 22 Component (C): Component (C1):Sartomer ® 399^(d)) 60 — — — Irgacure ® 184^(e)) 0.7 — — — Lucirin ®TPO^(e)) 0.3 — — — Butyl acetate 16 — — — Ethylethoxypropionate 16 — — —Methyl isoamyl ketone 5 — — — Byk ® 325 0.3 — — — Byk ® 358 0.7 — — —Tinuvin ® 292 0.5 — — — Tinuvin ® 400 0.5 — — — Component (C2) withoutisocyanate groups: Rahn ® 99-664^(f)) — 60 — 60 Irgacure ® 184 — 0.7 —0.7 Lucirin ® TPO — 0.3 — 0.3 Butyl acetate — 16 — 16Ethylethoxypropionate — 16 — 16 Methyl isoamyl ketone — 5 — 5 Byk ® 325— 0.3 — 0.3 Byk ® 358 — 0.7 — 0.7 Tinuvin ® 292 — 0.5 — 0.5 Tinuvin ®400 — 0.5 — 0.5 Component (C2) with isocyanate groups: Roskydal ®2337^(g)) — — 80 80 Ethyl ethoxypropionate — — 20 20 ^(a))commerciallycustomary leveling agents; ^(b))commercially customary lightstabilizers; ^(c))commercially customary polyisocyanate based onhexamethylene diisocyanate, from Bayer AG; ^(d))dipentaerythritolpentaacrylate from Cray Valley; ^(e))commercially customaryphotoinitiators; ^(f))commercially customary urethane acrylate fromRahn; hydroxyl number: 120 mg KOH/g; acrylate functionality: 3;^(g))commercially customary isocyanato acrylate from Bayer AG.

Despite very different material composition, the clearcoat materials ofexamples 1 to 4 were outstandingly suitable for the production ofclearcoats, especially as part of multicoat color and effect coatingsystems.

To produce the multicoat color and effect coating systems, sanded steelpanels were first of all coated with a commercially customarytwo-component polyurethane surfacer from BASF Coatings AG. The surfacerwas applied in two spray passes, dried at 60° C. for 30 minutes and thensanded. Subsequently, a commercially customary aqueous basecoat materialfrom BASF Coatings AG was applied in two spray passes and dried at 60°C. for 5 minutes. Thereafter, the clearcoat materials 1 to 4 wereapplied each in two spray passes with a flash-off time of 2.5 minutes inbetween.

The applied clearcoat films 1 to 4 were each flashed off briefly for 5minutes, dried at 60° C. for 15 minutes, and then cured using UVradiation with a dose of 1500 mJ/cm². The resultant clearcoats 1 to 4had a film thickness of from 50 to 60 μm. The multicoat systems ofexamples 1 to 4 had an outstanding appearance and intercoat adhesion.

In a second series of tests, the cure behavior of the clearcoatmaterials 1 to 4 in shadow zones of substrates was simulated by notcuring the above-described test panels using UV radiation. Nevertheless,the resultant clearcoats were not tacky, but instead had a good initialhardness.

1. A process for preparing a multicomponent system curable thermally andwith actinic radiation, comprising I) at least one of a) premixing atleast one liquid component (C) with a component (A) to form a mixtureA/C, and/or b) premixing the at least one liquid component (C) with acomponent (B) to form a mixture B/C, and II) mixing and homogenizing oneof i) mixture A/C with component (B), ii) mixture B/C with component(A), or iii) mixture A/C with mixture B/C, wherein component (A)comprises at least one constituent (A1) comprising per molecule onaverage at least two isocyanate-reactive functional groups, component(B) comprises at least one component comprising at least onepolyisocyanate (B1), component (C) comprises (C1) constituent (C1)comprising per molecule on average at least two functional groupscomprising at least one bond activated by actinic radiation, and (C2)constituent (C2) different from constituent (C1) comprising on averageper molecule at least one functional group comprising at least one bondactivated by actinic radiation, and on average per molecule at least oneisocyanate-reactive functional group or at least one isocyanate group.2. The process of claim 1, wherein the bonds activated with actinicradiation are selected from the group consisting of carbon-hydrogensingle bonds, carbon-carbon double bonds, carbon-carbon single bonds,carbon-oxygen double bonds, carbon-oxygen single bonds, carbon-nitrogensingle bonds, carbon-nitrogen double bonds, carbon-phosphorus singlebonds, carbon-phosphorus double bonds, carbon-silicon single bonds,carbon-single double bonds, and mixtures thereof.
 3. The process ofclaim 2, wherein the bonds activated by actinic radiation arecarbon-carbon double bonds.
 4. The process of claim 1, wherein thefunctional groups comprising at least one bond activated by actinicradication are selected from the group consisting of (meth)acrylate,ethacrylate, crotonate, cinnamate, vinyl ether, vinyl ester,ethenylarylene, dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl,allyl, butenyl, ethenylarylene ether, dicyclopentadienyl ether,norbornenyl ether, isoprenyl ether, iscopropenyl ether, allyl ether,butenyl ether, ethenylarylene ester, dicyclopentadienyl ester,norbornenyl ester, isoprenyl ester, isopropenyl ester, allyl ester, andbutenyl ester.
 5. The process of claim 1, wherein theisocyanate-reactive functional groups are selected from the groupconsisting of thiol, primary amino, secondary amino, imino, hydroxylgroups and mixtures thereof.
 6. The process claim 1, wherein constituent(C1) is a reactive diluent curable with actinic radiation and comprisingper molecule at least 5 bonds activated by actinic radiation.
 7. Theprocess of claim 1, wherein constituent (C2) comprises at least oneurethane acrylate having a hydroxyl number of from 50 to 200 mg KOH/g.8. The process of claim 7, wherein the urethane acrylate (C2) is admixedwith component (A).
 9. The process of claim 1, wherein the constituent(C2) comprises an isocyanate acrylate.
 10. The process of claim 9,wherein the isocyanate acrylate (C2) is admixed with component (B). 11.A multicomponent system curable thermally and with actinic radiation,comprising (A) at least one component comprising at least one thermallycurable constituent (A1) containing per molecule on average at least twoisocyanate-reactive functional groups, (B) at least one componentcontaining at least one polyisocyanate (B1), and (C) a compound (C)comprising at least one reactive diluent curable with actinic radiationand comprising per molecule at least 5 bonds activatable by actinicradiation, the reactive diluent (C1) not being introduced by way ofthixotropic agent, and a least one constituent (C2) different from theat least one reactive diluent (C1) comprising on average per molecule atleast one functional group comprising at least one bond activatable byactinic radiation, and on average per molecule at least oneisocyanate-reactive functional group or at least one isocyanate group.12. The multicomponent system of claim 11, wherein reactive diluent (C)comprises dipentaerythritol pentaacrylate.
 13. The multicomponent systemof claim 11, wherein the isocyanate reactive functional group comprisehydroxyl groups.
 14. The multicomponent system of claim 11, whereinconstituent (A) comprises at least one (meth)acrylate copolymer having ahydroxyl number of from 50 to 200 mg KOH/g.
 15. The multicomponentsystem of claim 11 made by the process of claim 1 which is a coatingmaterial, adhesive or scaling compound.
 16. A method of making a coatedsubstrate, comprising applying the multicomponent system of claim 11 toa substrate selected from the group consisting of automotive OEMfinishing substrates, automotive refinishing substrates, furnituresubstrates, door substrates, window substrates, interior substrates,exterior substrates, industrial coating substrates, coil coatingsubstrates, container coating substrates, f electrical componentssubstrates.
 17. The method of claim 16, wherein the multicomponentsystem is applied wet-on-wet and the coated substrate has a colored oreffect appearance.
 18. The process of claim 1, wherein constituent (C1)is present in compound (C) in an amount from 30% to 90% by weight, andconstituent (C2) is present in compound (C) in an amount from 60% to 95%by weight.
 19. The multicomponent system of claim 11, wherein thereactive diluent is present in compound (C) in an amount from 30% to 90%by weight, and constituent (C2) is present in compound (C) in an amountfrom 60% to 95% by weight.